Azo dyestuff



Patented June 27, 1933 UNITED STATES PATENT FFICE FRIEDRICH ormonLEVEBKUSE'N NEAR eoLoeNE-cn-Trrn-RHINE, ennivmnr, AS-

,SIGNOB. 'ro GENERALANILINE WORKS, rim, ornnw YOBILN. Y., A CORPORATIONQF DELAWARE AZO DYESTUFIE No Drawing. Application filed March 26, 1931,Serial No. 525,625, and in Germany April 1, 1930.

The present invention relates to new water insoluble azo dyestuffs, moreparticularly it relates to dyestuffs which are obtainable by couplingeither in substance or on a substratum or on the fibre'a diazotizedamino compound capable of producing an azo dyestuff which amine itselfmay contain an azo bridge with an arylamide of aQ-hydroxyphenanthrene-3-carboxylic acid or of a8-hydroxyphenanthrene-Q-carboxylic acid, the components being selectedin such a manner that none of them contains the sulfonic acid orcarboxylic acid groups. As amines coming into considerationfor thepurpose of this invention there may be mentioned by way of exampleamines of 'the'benzene and naphthalene series, amino carbazoles, aminodiphenylene-oxide etc.

My new azo dyestufis may be represented by the probable general formulaX V wherein It stands "for the residue of a diaZotizationcomponentcapable of producing an azo dyestufi, one X stands for ahydroxy group andtheother X stands for the group CONHaryl" and whereinthe nuclei may be substituted with the exception oif'a, sulnucleus infonic acid or carboxylic acid group, for example by alkyl, oxalkyl,alkyl-hydroxy, halothe nitro group etc., and wherein n representsone'ofthe numbers 1 and 2, the azo bridge being attached to thephenanthrene ortho position to the hydroxy group. 4 The method of.manufacture of thephy droxyphenanthrene o-carboxylic acids isdescribed'by Verner, in Berichte der Deutsohen Chemischen Gesellschaft,vol. 35, page 4423,

The arylides of these acids are for instance obtainable bycondensing atboiling tempera- V ture in an inert organic solventor diluent,

such as toluene or Xylene in thepresence of a condensing agent such asphosphorous oxy-, chloride, the I, hydroxyphenanthrene ocarboxylic acidand the aromatic base.

The new dyestuffs possess the most varied shades, depending on thespecific amine used which shades when produced on the fibre exhibit goodfastness properties.

The invention is illustrated by the followwhich has been neutralized bymeans of sodium acetate and which contains 2 grams of2.5-dichloroaniline per litre, thenojwashed and soaped. In this mannera'fast yellowish red is obtained, the dyestufi' having the followingformula:

The 2-hydroXyphenanthrene-3-carboxylic acid-o-toluidide yields with:-l-nitraniline, a' brown; 5-nitro-o-anisidine, a reddish violet;5-chloro-2-toluidine, a Bordeaux red; maminoazo-toluene N112 I i I abrown; Q-amino-5-benzoylamino-hydroquinone diethylether, a navy blue;dianisidine, a reddish blue; l-aminocarbazole, a violet-brown,Q-aminocarbazole, a black; 9-

oethyl-3-aminocarbazole, a black; Z-arninodiphenylene-oxide, areddish-brown.

.. Example 2.In an analogous manner to that of Example 1, the3-hydroxyphenanthrene-Q-carboXylic acid-o-toluidide yields with2.5-dichloro-aniline a dyestufi' of the formula 15 a Bordeaux red;5-nitro-o-anisidine, a greenish black m-zimino-azo-toluene, ablackishbrown; 2-amino-5-benzoylamino-hydroquinone-diethylether, agreenish-blue; 1 -amino carbazole, a violet brown; Q-aminocarbazole, ablack; 3-aminocarbazole, a black; 2-aminodiphenylene-oxide, a violetbrown.

Example 3.In an analogous manner to that of Example 1, the3-hydroxyphenanthrene 2 carboxylic acid para anisidide yields with:5-nitro-2-anisidine, a reddishblack; t-nitro-o-toluidine, a Bordeauxred; 2. 5-dichloro-aniline, a Bordeaux red; i-chloro-o-nitroaniline, 'abrown; 3-nitro-p-tolui- 3U dine, a brown; 4-nitro-2-5-dimeth0xy-4-inocarbazole, a black. 7

Example 4.In an analogous/manner to "that described in Example 1, the2-hydroxyphenanthrene-3-carboxylic acid-fl-naphthylamide yields with2-aminoca-rbazole a black, the dyestufl having the following formulaO/UO (EQEQ 8 I claim I v I AS new Products azo dyestufi's of'theprobable general formula v wherein nstands for one of the numbers 1 Vand 2, R stands for the residue of a diazotization component capable offorming an azo a dyestufi, one X stands for a hydroxy group and theother X stands for the group CO.NH.aryl, theazo bridge being attached 9to the phenanthrene nucleus in ortho positIOII tO tlI Q hydroxy groupand wherein all nuclei maybe substituted by ,substituents of the groupconsisting of alkyl, oxalkyl, al-" koxy, halogen and the nitro group,being va- 35 nous colored powders and yielding when probable generalformula aminoazobenzene, a greenish-black; 2-am- I of good fastnessproperties.

2. As new products azo dyestuffs of the wherein n stands forone of thenumbers 1 and 2, R stands for the residue of adiazo- (JO-NH-aryltization component capable of forming an azo dyestuif, aryl stands foran aromatic residue of the benzene or naphthalene series and wherein allnuclei may be substituted 'by substituents of the group consistingofalkyl, oxalkyl', alkoxy, halogen and the nitro group, being variouscoloredpowders and yielding when produced on the fibre the most variedshades ofgoodfasb" ness properties.

3. As anew formula product the dyestufi ofthe wherein n stands for oneofthe numbers 1 and 2, R stands for the residue of a diamtizationcomponent capable of forming an azo dyestufi', aryl? stands for. anaromatic residue of the benzene or naphthalene series and wherein allnuclei may be substituted by substituents of the group co i t 1 ing ofalkyl,"oxa1kyl, alkoxy, 'lialogen'and thenitro group, being variouscolored powders and yielding when produced on the fibre the mostvariedshades of good fastness'properties.

' 5. As a new product the dyestufi of the formula yielding when producedon the fibre Bordeaux red shades of good fastness properties.

6. Fiber dyed with a dyestulf as claimed in claim 1. 7. Fiber dyed withadyestufi as claimed in claim 2.

8. Fiber dyed with a dyestufl as claimed in claim 3. I I 9. Fiber dyedwith a dyestuif as claimed in claim 4.

10. Fiber dyed with a dyestuif as claimed in claim 5. v

In testimony whereof, I afiix my signature. FRIEDRICH MUTH.

